Porous acidic resin catalyst, preparation method and applications thereof

Abstract

The present invention provides a porous acidic resin catalyst, wherein a nanometer material adopted as a pore forming hard template agent is directly doped into a macromolecule resin, reaction dissolving is performed in an acid solution to remove the nanometer material so as to form nanometer pore channels in the macromolecule resin, and then a sulfonation reaction is performed to achieve acid functionalization so as to prepare the nano-pore resin solid acid. The present invention further provides a preparation method and applications of the porous acidic resin catalyst. According to the present invention, the porous acidic resin catalyst has characteristics of large pore volume, large specific surface area, and strong acidity; and with the application of the porous acidic resin catalyst as the solid acid catalyst in the catalytic reaction for esterification synthesis of sec-butyl acetate from acetic acid and butene, the reaction activity is high, the reaction stability is good, and the butene conversion rate and the sec-butyl acetate yield of the esterification reaction can be significantly improved.

Description

technical field [0001] The invention belongs to the field of catalyst preparation, in particular to a porous acidic resin catalyst used for esterifying acetic acid and butene to synthesize sec-butyl acetate. Background technique [0002] Acetate is catalyzed direct addition and esterification of propylene, 1-butene, 2-butene, isobutene and other lower alkenes with acetic acid or other carboxylic acids to produce corresponding isopropyl acetate, sec-butyl acetate and isobutyl acetate Esters and other acetates and other carboxylates. At present, the products with the broadest market prospects are isopropyl acetate and sec-butyl acetate. [0003] Secondary butyl acetate, also known as additional butyl acetate, second butyl acetate, is one of the four isomers of butyl acetate, a colorless, flammable, fruity liquid, and other isomers Performance is similar in most cases and can dissolve a wide variety of resins and organics. Its boiling point is lower than that of commonly use...

AI Technical Summary

Problems solved by technology

[0005] CN101544562A has invented a method for zeolite molecular sieve to catalyze acetic acid and butene to synthesize sec-butyl acetate, using butene and acetic acid as raw materials, using modified beta zeolite molecular sieve as catalyst, and continuously synthesizing sec-butyl acetate in a fixed-bed reactor; However, the zeolite molecular sieve catalyst is easy to form carbon at the reaction temperature of 90-130°C, and the reaction deactivation is relatively fast. Therefore, although it does not have the strong corrosiveness and toxicity of sulfuric acid, the catalyst has the problem of poor long-term use stability, which restricts its industrial application

However, the ordinary styrene-divinylbenzene cation exchange resin itself has small pore volume and specific surface area, and a small amount of acid on the pore surface, which causes the problem that its reaction diffusion as a solid acid catalyst is limited, so that it is used in heterogeneous catalysis. Low reactivity and selectivity in application

Chinese patent CN101948385A has proposed a kind of synthetic method of sec-butyl acetate, and the used catalyst of reaction is macroporous strongly acidic cation exchange resin; Because common macroporous strongly acidic cation exchange resin specific surface area is less, catalytic activity and raw material single-pass conversion rate are relatively Low, must be operated under pressure, raw materials acetic acid and C 4 All olefins pass through three fixed-bed reactors continuously in the same direction in the liquid state, and the cycle used is relatively large, so the energy consumption and material consumption are high, which affects its economy.

By introducing electron-withdrawing groups such as F, Cl, and Br on the benzene ring, the high temperature resistance of the styrene-based strong acid resin catalyst is improved, but the specific surface area of ​​the resin catalyst is still low (30-50m 2 / g), resulting in low reactivity, easy scaling and rapid deactivation

[0008] From the above-mentioned analysis of the existing acetic acid and butene esterification synthesis technology and the preparation method of cationic acidic resin catalyst, the problem that currently restricts the realization of industrial application of resin solid acid to replace liquid acid is mainly that the specific surface area of ​​resin catalyst is still low (30-50m 2 / g), resulting in low reactivity and poor reaction selectivity, which cannot meet the requirements of esterification application as a heterogeneous catalyst.